Ceramic frit composition



United States Patent '0 2,918,383 CERAMIC FRIT COMPOSITION James H..Strimple, Milltown,;N.J., assignor to National Lead Company, New York,-N;Y., a corporation of New Jersey N Drawing. Application March 21, 1957 Serial No. 647,484 3 Claims. (Cl. 106-48) .Thisinvention relates in general to frit compositions. More specifically, this invention relatestothe preparation of frit compositionsfrom which colored porcelain enamels'may be produced.

Many types of frit compositions have been produced which form colored porcelain enamels when sprayed and These frit compositions vary .considerably in chemical composition and most any type and color of porcelain enamel hasbeenJproduced by a variety of methods. This invention is primarily concerned with frit compositions which are opacified with titanium dioxide and which form pink porcelain enamels upon firing.

Colored porcelain enamels usually are produced by adding, as a mill addition, a color stain as the coloring agent. However, in forming a 'pinkenamel color stains added as mill additions are not1suitable when a titania opacified frit composition is employed. Although cornbinations of chromium and tin compounds have been .used as stains in forming pink enamels, these stains are .not suitable when used with titania opacified frit compositions.

Another type of coloring agentemployed for producing colored porcelain enamels are those which are added as one of the ingredients in the frit composition itself.

.These coloring agents are present in the frit composition in varying amounts to produce the desired color effect in .the porcelain enamels formed upon firing. Injtitania opacified frit compositions, small amountsof'gold have been added as an ingredient to produce a pink porcelain enamel. Two disadvantages, however, are encountered with this method; gold is an expensive ingredient, and the pink color obtained in theporcelain enamel is variable. This method is undesirable to use, therefore, since the pink color will vary from-batch to batch, thus making it difficult to obtain pink colors which will match. .It is desirable, therefore, to develop a titania opacified .frit composition which, when fired, produces reproducible pink porcelain enamels.

An object of this invention, therefore, is to produce a new and novel .titania opacified frit composition which produces a pinkporcelainenamel upon firing. A further object is to produce an economical fritcomposition which, when fired, produces'a reproducible pink enamel. ZThese andother objects willbecome apparent from the following more complete description of the instant invention.

Broadly, this invention contemplates a titania opacified frit composition, capable of forming a pink porcelain enamel upon firing, said composition consisting essentially of the following ingredients:

Mole 'percent metal surface in the usual manner.

2,918,383 Patented Dec. 22, 1959 The frit composition @of the instantinvention is prepared by any standard method. For example, the raw materials are mixed thoroughlytogether and the mixture is melted. The molten Lmixture is then poured into water to form the frit.

The raw materials used are all standard ceramic grade materials employed in making various frit compositions; however, it is necessary to add the raw materials in quantities to produce the necessary critical amounts in the frit produced. Each ingredient must be present in the amounts specified above or undesirable results will be obtained.

The combination of cadmium sulfide and selenium is used as the coloring agent in the'fritlcomposition to produce the desirable pinkcolorinthejporcelain enamel. This coloring agent may'be added .to the frit batch as cadmium sulfide and selenium metal 101 as a cadmium sulfoselenide compound. This combination should be added in amount to produce in the :frit composition amounts .from 0.1 to 2.0% :forthecadrnium sulfide and from 0.05% to 1.0% for the-selenium.

Although various tones and shades of pink ranging from peach to coral are obtained by varying the amounts of the ingredients in the frit composition within the ranges specified above, all of these products are pleasing to the eye and are reproducible from batch to batch.

The mixture of raw materials used in preparing this type of frit composition-melt in the temperature range of 1250 C. to 1350? C. The frit composition formed from the mixture is then ground and mixed with standard mill additions to form ..a..slip and the slip is sprayed onto a The coated surface is then firedto. form. the pink porcelain enamel.

In order tomore full-y illustrate the instant invention, the followingexamples are presented.

EXAMPLE I A frit composition was prepared by melting together for about -1 hour atabout 1350 C., a mixture of the following ingredients:

Parts by wt.

Potassium fluosilicate 3.3 Monobasic sodium phosphate 32.1 Borax (anhydrous) 24.3 Orthoboric .acid 67.2 Potash 30.3 Zinc carbonate 45 .3 Titanium dioxide 34.5

Potters flint 123.9 Cadmium sulfide 1.86 Selenium metal powder 0.51

Upon obtaining complete intersolution of the ingredients, the melt was quenched in water to form a frit havmg the following composition:

Component Mole Weight Percent Percent One hundred parts of this quenched frit were ball milled for 16 hours with 4 .parts .of clay, 0.125 part NaNO 0.3 part K CO .and 40 parts demineralized water. The milled frit wasthenstrained through a mesh screen to remove any coarse particles. The

if I lb EXAMPLE X what with the combination and amounts of agents employed.

A frit composition was made which was substantially identical to the frit composition produced in Example I and upon firing the color of the porcelain enamel matched the color of the enamel produced in Example I.

Table 1 2,918,383 a 3 strained slip was well dispersed and of sprayable consistency.

They were air dried The milled slip was then sprayed onto four cobalt ground-coated steel panels at a dry application weight of about grams per square foot. followed by drying at 110 C. for 15 minutes, and then fired under oxidizing conditions (air atmosphere) at 790 0., 815 C., and 840 C. for three minutes. The re- From the above description and by the examples presented, it has clearly been shown that reproducible and uniformly pink porcelain enamels have been produced from a titania opacified frit composition.

The cadmium sulfide and selenium used as the coloring ingredients in the enamel frit composition are employed in sufficiently small amounts to make it possible to 8 51.320320 00 0 764 370.4000 4874227899 0 N 1 l l p nnumnhm m p o m m p m n ssnoo m 0 m 1 mm mm 1 C a a a X X X E E E m m5511724 H .W 548704 meow MM 0092340 11 0 k I .Lxmomnad d fi I 5 I 5 6 3womL 0 mn .3263432 1 m 5 mnzmeo 0 u 5 1 87 00 0 a 1 a 4 a 1 P V V V E u E u E N 9532162 m3 W. 6543704 W0 W 3190301 98 0 mn 2634 3 m mH w m m mu 5 m 87 00 m 0 V V V C X X X E n E n E t .m. 7.9304515 73 m 2548704000 um 5196391899 0 k L t 06.3fm m 3%52450. 1 .t m aheufimnzuoolnal U m 4 1 m M .m .1 8V 1 n aV a 1 P e X MW x x r W E u E m E V. P b M. 63665634 4 3 B .M 0544700000 M m 1191354899 0 .m S .l mv 3262531 U 0 mv M m mw m mv w0 w m 8 a 1 M a e a 1 w P P X 2 X X E E 3 E m. 6 809919 36 m M. 4543 m04000 .w m 8080 49799 0 .w mV 3 H 1 n m m mmfil oll 0 mV 63 m86100 m a1 a1 001 X X n T. X n P E E u E u m 35423724608 M 25437040050 .W 79842287544 0 .K .0104 m 3 1 mn 55m2m811 mn 53 1861004 0 m an 1 T. 31 .1 X X ,X E E E .M 35363722 m 5543704084 um 3087349835 m 0 m m 33263432 41 m 55 2m8100 mI 63- 186100 0 H 1 1 1 a1 1 X X X E E E u u u Q u n n u n u n u n n n n 0 u m m n u n u n n a n D :W E S f. D .h 0 B .p. n "w u u "L L L m m. m h u u "M w m h m m w "w S S L C 0 m u e a o mw "ma rt. fl nfiM .mo u moth w m M ma mhm m S ar m m lv a mu b ll 1 o ofi mfl m unmhncntm n tortt i t k 0 Grow 71 .1 PMBoPzTPLCs produce pink enamels more economically than by using gold as the coloring agent.

Furthermore, the use of the frit composition of the 2 d 3 instant invention is more desirable than using a frit comtion has been described and illustrated position containing gold since reproducible colors are obtained using the frit compositions of the instant invention.

While this inven The shade and tone of the color obtained varied some 75 by the examples shown, it is not intended to be strictly 5 6 g oe mmam md ea d ob m m oum a w Ii d e w dw d m m mmn ph k etina r. uh m wm e t. me r ermem Wa E mh Lbrrhe uuP m Mm fl m mm A o W Ece.mMw 1w wha r- L mm m c m ce .la nnr r l .CSD. Sb S u m m W A n o ma tEf I frit compositions are recorded in Tables 1,

Porcelain enamels were formed from all of these frit compositions using the procedure described in Example I and the resulting porcelain enamels were all smooth, continuous, durable enamels having uniform pink colors.

limited thereto, and other variations and modifications may be employed within the scope of the following claims.

I claim: 1. A frit composition capable of forming a reproducible pink porcelain enamel, said composition consisting essentially of:

Mole percent SiO, 40-50 N320 5-7 K 0 5-7 Li O 0-2 B 0 15-19 P 0 0-3 TiO 8-15 ZnO 7-11 F, 0-7 CdS 0.1-2.0 Se 0.05-1.0

References Cited in the file of this patent UNITED STATES PATENTS 2,414,633 Bryant Jan. 21, 1947 2,514,855 Goetchins Jan. 11, 1950 2,706,692 Chester Apr. 19, 1955 2,753,271 Treptow July 3, 1956 OTHER REFERENCES I. H. Koenig et al.: Literature Abstracts of Ceramic Glazes (1951), pages 54, 59, 207, 265, 334.

W. W. Cofieen: Enamel Bibliography and Abstracts (1956), columns 112d, 114i and 980. 

1. A FRIT COMPOSITION CAPABLE OF FORMING A REPRODUCIBLE PINK PORCELAIN ENAMEL, SAID COMPOSITION CONSISTING ESSENTIALLY OF: 